Flowable nondigestible oil and process for making

ABSTRACT

A flowable nondigestible oil composition having a Consistency in a temperature range of 20° C. to 40° C. of less than about 600 P.sec(n-1), preferably less than about 400 P.sec(n-1). The flowable nondigestible oil contains a liquid polyol polyester having a complete melt point less than 37° C., and a solid polyol polyester having a complete melt point of at least about 37° C. The solid polyol polyester can be a solid saturated polyol polyester, a solid diversely esterified polyol polyester, a polyol polyester polymer, or a combination thereof, which are crystallized, or co-crystallized, into unaggregated crystal particles of typically less than 10 microns in maximum dimension. The flowable nondigestible oil is made by a process which includes the steps of melting completely the nondigestible oil, crystallizing the solid polyol polyester while applying shear to avoid formation of clusters of crystallized aggregates which can prevent the composition from being flowable. A preferred equipment for crystallizing the solid polyol polyester to form the flowable composition is a scraped wall heat exchanger.

FIELD OF THE INVENTION

This invention relates to a nondigestible oil containing a solidnondigestible oil component, which can flow at ordinary and ambientstorage temperatures, and to a process for making the flowablenondigestible oil.

BACKGROUND ART

Numerous patents have been directed to providing materials which havethe physical and gustatory characteristics of triglyceride fats, butwhich are absorbed to a low extent or not at all by the body. Thesematerials are referred to variously as noncaloric fats, pseudofats,nondigestible fats and fat substitutes. Patents pertaining to suchmaterials include U.S. Pat. No. 4,582,927. Fulcher, issued Apr. 15,1986, (fatty esters of malonic acid); U.S. Pat. No. 4.582,715.Volpenhein, issued Apr. 15, 1986, (alpha acetylated triglycerides); andU.S. Pat. No. 3,579,548, Whyte, issued May 18, 1981. (triglycerides ofalpha-branched chain carboxylic acids).

One particular type of compound which has achieved considerableattention as a nondigestible fat is sucrose polyester (i.e., sucrose inwhich at least four of the eight hydroxyl groups are esterified with afatty acid). U.S. Pat. No. 3,600,186, Mattson, issued Aug. 17, 1971;U.S. Pat. No. 4,368,213, Hollenbach et al. issued Jan. 11, 1983; andU.S. Pat. No. 4,461,782, Robbins et al. issued Jul. 24, 1984 describethe use of this material as a nondigestible fat in a variety of foodcompositions.

A problem associated with use of liquid nondigestible oils, i.e., thosehaving a melting point below body temperature (about 37° C.), is anundesired passive oil loss effect, which is manifested in leakage of theliquid nondigested fat through the gastrointestinal tract's analsphincter. Regular ingestion of moderate to high levels of completelyliquid forms of these polyol polyesters can produce this passive oilloss. U.S. Pat. No. 4,005,195, Jandacek, issued Jan. 25, 1977, disclosesthe combining of higher melting fatty materials such as solidtriglycerides and solid sucrose polyesters with the liquid sucrosepolyesters in order to control oil loss.

U.S. Pat. No. 4,797,300 (Jandacek et al.), issued Jan. 10, 1989discloses the use of certain solid sucrose polyesters which have highoil binding capacity for liquid sucrose polyesters (SPE) and liquidtriglycerides, when used at levels of about 10% to 25% in said oils. Itis disclosed that because of their high oil binding capacity, thesesolid sucrose polyesters have outstanding utility as agents to preventpassive oil loss of liquid nondigestible sucrose polyesters, and theyare also useful as non-caloric hardstocks to use with liquid digestibleor nondigestible oils in the preparation of semi-solid fat products suchas shortenings and margarines. The oil binding agents of the Jandacek etal. '300 patent are solid sucrose polyesters wherein the ester groupsconsist essentially of a mixture of short chain saturated fatty acidester radicals (C₂-C₁₀) and long chain saturated fatty acid radicals(C₂₀-C₂₄) in a molar ratio of short chain to long chain of from about3:5 to about 5:3, and wherein the degree of esterification is from about7 to about 8. Jandacek et al. also disclose plastic shortening and otherfood compositions containing 10-25% of the solid SPE.

U.S. Pat. No. 4,005,195 (Jandacek), issued Jan. 25, 1977 describes ameans of preventing the undesirable oil loss effect through the additionof the polyesters as oil-loss control agents. The oil-loss controlagents include solid fatty acids (melting point 37° C. or higher) andtheir triglyceride sources, and solid polyol fatty acid polyesters.Specifically C₁₀-C₂₂ saturated fatty acid polyesters are said to beuseful at levels of at least 10%, preferably at least 20%.

U.S. Pat. No. 5,306,514 (Letton et al.), issued Apr. 26, 1994, disclosesedible oil compositions containing a) a liquid nondigestible oil havinga complete melting point below about 37° C. and b) a solid polyol fattyacid polyester having a complete melting point above about 37° C.,wherein the weight ratio of b) to a) is from about 1:99 to about 9:91.The solid polyol fatty acid polyester consists of (i) a polyol having atleast about 4 hydroxyl groups, wherein at least about 4 of the hydroxylgroups of the polyol are esterified, and (ii) ester groups comprised of(a) fatty acid radicals selected from the group consisting of C₁₂ orhigher unsaturated fatty acid radicals, C₂-C₁₂ saturated fatty acidradicals, or mixtures thereof, and (b) C₂₀ or higher saturated fattyacid radicals, at a molar ratio of (a):(b) being from about 1:15 toabout 1:1. In the solid polyol polyester at least 15% by weight of thefatty acid radicals C₂₀ or higher saturated fatty acid radicals.Further, the slope of the SFC profile of the mixture of a) and b)between 37° C. and 21.1° C. is between 0 and about −0.75.

U.S. Pat. No. 5,306,515 (Letton et al.), issued Apr. 26, 1994, disclosespourable compositions containing a solid polyol fatty acid polyester,having a complete melting point above about 37° C., a liquidnondigestible oil having a complete melting point below about 37° C.,less than about 90% by weight of a digestible oil having less than 5%solids at 21° C.; and less than 10% hardstock; wherein the ratio of (A)to (B) is from about 1:99 to about 9:91 and wherein the pourablecomposition has a yield point of not more than about 100 dynes/cm². Thesolid polyol fatty acid polyester consists of (i) a polyol having atleast about 4 hydroxyl groups, wherein at least about 4 of the hydroxylgroups of the polyol are esterified, and (ii) ester groups comprised of(a) fatty acid radicals selected from the group consisting of C₁₂ orhigher unsaturated fatty acid radicals, C₂-C₁₂ saturated fatty acidradicals or mixtures thereof, and (b) C₂₀ or higher saturated fatty acidradicals at a molar ratio of (a):(b) being from about 1:15 to about 2:1.In the solid polyol polyester at least 15% by weight of the fatty acidradicals are C₂₀ or higher saturated fatty acid radicals. Further, theslope of the SFC profile of the mixture of (A) and (B) between 37° C.and 21.1° C. is between 0 and about −0.75, and the combined level of (A)and (B) in said composition is at least 10% by weight. Examples includecompositions containing 65 wt. % liquid digestible triglyceride oil.

It is an object of the present invention to provide a flowablenondigestible oil composition containing a solid at ambient temperaturewhich is flowable at ordinary and ambient temperatures, and which cansubsequently be used as an edible nondigestible oil providing goodpassive oil loss control and good organoleptic properties to foodsprepared with them.

SUMMARY OF THE INVENTION

A flowable nondigestible oil composition of the present inventioncomprises a) a liquid polyol fatty acid polyester having a complete meltpoint less than 37° C., and b) a solid polyol fatty acid polyesterhaving a complete melt point of at least about 37° C. The flowablenondigestible oil has a Consistency (K) within the temperature range of20-40° C. of less than about 600 P.sec^((n−1)), where K is determinedfrom a power law model fit of the apparent viscosity versus shear ratedata (see Analytical Method Section), and n is the shear index(dimensionless). Preferably, the flowable nondigestible oil has aConsistency of less than about 400 P.sec^((n−1)) at a temperature rangeof 20-40° C. The flowable nondigestible oil composition contains thesolid polyol fatty acid polyester in the form of small crystalparticles, typically having a largest dimension of less than about 30microns, preferably less than about 10 microns, more preferably between1 and 30 microns, even more preferably between 1 and 10 microns,and mostpreferably of about 2 to about 5 microns.

The present invention also provides a process for making a flowablenondigestible oil, wherein the nondigestible oil comprises a) a liquidpolyol fatty acid polyester having a complete melt point less than 37°C., and b) a solid polyol fatty acid polyester having a complete meltpoint of at least about 37° C. The process comprises the steps ofmelting completely the nondigestible oil composition containing thesolid polyol fatty acid polyester, rapidly cooling the meltednondigestible oil to a crystallization temperature, thereby rapidlycrystallizing at least a substantial portion of the solid polyol fattyacid polyester, and shearing the nondigestible oil composition duringthe step of crystallizing to form the flowable nondigestible oilcomposition. Optionally, following the crystallizing and shearing steps,the process can include the step of tempering the crystallizednondigestible oil composition for a time sufficient to substantiallycompletely crystallize all of the solid polyol fatty acid polyester, thestep of adding a stabilizing amount of a diluent liquid, typically aliquid polyol fatty acid polyester, to the crystallized nondigestibleoil composition, or both steps.

These compositions are capable of being stored in a flowable state atambient and ordinary storage temperatures. Storage at ambient andordinary temperature avoids exposure of the composition to hightemperatures (generally greater than 50° C.) usually associated withstorage and handling of the nondigestible oil composition in a moltenform. Making and storing the nondigestible oil in a flowable form allowsthe nondigestible oil to be easily handled at ambient handling andstorage temperatures, which minimizes the effect of heat and hightemperature on the chemical stability of the polyol fatty acidpolyester. This results in greater oxidative and flavor stability duringextended storage of the nondigestible oil and of food productscontaining the nondigestible oil. This is particularly advantageous whenthe liquid polyol fatty acid polyester component of the nondigestibleoil is made from an un hardened (non-hydrogenated) source oil, such asunhardened cottonseed oil. In addition, the flowable nondigestible oilof the present invention can be utilized as a carrier for theapplication or incorporation of ingredients to foods products, such asflavorings, seasonings, and vitamins.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1a through 1 c depict sucrose octaester monomer, dimer and trimer,respectively.

DEFINITIONS

As used herein the term “nondigestible” shall mean being absorbable toan extent of only 70% or less (especially 20% or less) by the human bodythrough its digestive system.

As used herein, the term “flowable” refers to ability of a compositionto be transported by gravity or by conventional mechanical or pneumaticpumping means from a storage vessel.

As used herein the term “ambient” shall mean a temperature which is lessthan the lowest onset crystallization temperature of a solid polyolfatty acid polyester in the nondigestible oil composition.

As used herein, the term “food” refers to any manner of viand for usageby man. “Food” may further include individual food components ormixtures thereof.

As used herein, the term “comprising” means various components can beconjointly employed in the fat compositions of the present invention.Accordingly, the term “comprising” encompasses the more restrictiveterms “consisting essentially of” and “consisting of”.

All percentages and proportions herein are by weight unless otherwisespecified.

DETAILED DESCRIPTION OF THE INVENTION

High temperatures and exposure to oxygen can result in thermal andoxidative composition of the nondigestible oil composition. It ispreferred to avoid storage and handling of the nondigestible oil at thehigher temperatures provided in heated railway cars and productiontanks, which are needed to maintain the nondigestible oil in a moltenstate.

Consequently, there is a significant advantage to store and transportthe nondigestible oil at lower, ambient temperatures, and in the absenceof oxygen, to inhibit or reduce thermal and oxidative degradation of thenondigestible oil composition, to improve the quality of thenondigestible oil composition and the foods prepared therewith, and torequire less expensive and less complicated transportation and storagerequirements for the nondigestible oil composition. Generally, theambient temperature at which the flowable nondigestible oil of thepresent invention would be stored is from about 5° C. to about 50° C.,and more preferably from about 20° C. to about 40° C.

To commercially process the nondigestible oil economically and in largequantities, there is a need for a rapid process to make a flowablenondigestible oil composition which can be handled and stored at ambienttemperature. Typically such a process would convert the nondigestibleoil into a flowable nondigestible oil at ambient conditions in less than2 hours, preferably in less than one hour, and more preferably in lessthan 30 minutes. For commercial reasons, the flowable nondigestible oilcomposition of the present invention should have good flow properties,such that the flowable nondigestible oil will drain sufficiently,preferably substantially completely, by the force of gravity from theinside of transportation vessels, such as railway cars, andmanufacturing containers, such as tanks. Preferably, the flowablenondigestible oil composition of the present invention generally willnot adhere in a mass to the side walls and other surfaces inside therailway cars or tanks. That is, the flowable nondigestible oil willtypically drain such that only a relatively thin layer or film of thenondigestible oil will remain on the inside surfaces of a vessel ortank. Preferably, the flowable nondigestible oil is stable duringextended storage; that is, it remains flowable and there is minimal andpreferably no separation or settling of the solid crystals.

A. Composition of Flowable Nondigestible Oil

A flowable nondigestible oil composition comprising a solid polyol fattyacid polyester having a complete melting point of at least about 37° C.and a liquid polyol fatty acid polyester having a complete melting pointof less than about 37° C., can be prepared which is flowable at ambientstorage temperatures, and can, upon further processing includingremelting completely the solid polyol fatty acid polyester, provide goodpassive oil loss control and organoleptic properties (i.e. goodmouthfeel) to foods prepared therewith. The flowable nondigestible oilcomposition of the present invention generally comprises about 50% toabout 99%, more preferably about 80% to 97%, and most preferably about85% to 95%, of the liquid polyol fatty acid polyester. The flowablenondigestible oil composition of the present invention generallycomprises about 1% to 50%, more preferably about 3% to 20%, and mostpreferably about 5% to 15%, of the solid polyol fatty acid polyester.

The flowable nondigestible oil composition generally has a Consistencyof less than 600 P.sec^((n−1)) in a temperature range of from 20-40° C.The flowable nondigestible oil composition will have a Consistency ofpreferably less than about 400 P.sec^((n−1)), more preferably less thanabout 200 P.sec^((n−1)), and most preferably less than about 100P.sec^((n−1)), in a temperature range of 20-40° C.

Mixtures of solid polyol polyesters of the invention with liquidnondigestible oils are further characterized in having a relatively flatsolids content profile across the temperature range of from typical roomtemperature to body temperature, i.e., from about 21.1° C. (70° F.) toabout 37° C. (98.6° F.). The slope of the SFC profile is expressed asthe change in percent solids per unit change in temperature, in ° F.Typically the slope of the Solid Fat Content (SFC) profile between thesetemperatures is between 0 and −0.75. Generally, the greater the weightpercent of C₂₀ or higher saturated fatty acid radicals in the solidpolyol polyester, the flatter the SFC profile slope will be. Forexample, at the 30% C₂₀ or higher fatty acid level the slope willtypically be between 0 and −0.5, and at 50% it will typically be between0 and −0.3.

Determination of SFC values over a range of temperatures can be done bya method involving PNMR (Pulsed Nuclear Magnetic Resonance). Such methodis well known to those skilled in the art (see J. Amer. Oil Chem. Soc.,Vol. 55 (1978), pp. 328-31, and A.O.C.S. Official Method Cd. 16-81,Official Methods and Recommended Practices of The American Oil ChemistsSociety, 3rd. Ed., 1987; both incorporated herein by reference).

1. Solid Polyol Fatty Acid Polyester

The solid polyol fatty acid polyester of the present invention will havea complete melt point of at least 37° C., which is the ordinary bodytemperature, and more preferably of at least 50° C., and most preferablyof at least 60° C., and less than 500° C. Preferably, the solid polyolfatty acid polyester is selected from (i) a solid saturated polyolpolyester, (ii) a solid diversely esterified polyol polyester, (iii) apolyol polyester polymer, and (iv) combinations thereof.

The polyols which are used in the solid polyol polyester compounds ofthe present invention preferably contain from about 4 to about 12, morepreferably 4 to 8, most preferably 6 to 8, hydroxyl groups. Examples ofpreferred polyols are sugars (including monosaccharides anddisaccharides and trisaccharides) and sugar alcohols, containing from 4to 11 hydroxyl groups. The trisaccharides raffinose, and maltotriose areexamples of sugars which contain 11 hydroxyl groups. The preferredsugars and sugar alcohols are those which contain 4 to 8, morepreferably 6 to 8, hydroxyl groups. Examples of those containing fourhydroxyl groups are the monosaccharides xylose and arabinose and thesugar alcohol erythritol. Suitable five hydroxyl group-containingpolyols are the monosaccharides galactose, fructose, mannose andglucose, and the sugar alcohol xylitol. A polyol containing six hydroxylgroups is sorbitol. Examples of disaccharide polyols which can be usedinclude maltose, lactose, and sucrose, all of which contain eighthydroxyl groups. Examples of other suitable polyols are pentaerythritol,diglycerol, triglycerol, alkyl glycosides, and polyvinyl alcohols. Thepreferred polyol is sucrose.

The average degree of esterification of the solid polyol fatty acidpolyesters is of at least 4 ester groups, i.e., at least 4 of thehydroxyl groups of the polyol are esterified with fatty or other organicacids. Polyol esters that contain 3 or less ester groups are generallydigested in (and the products of digestion are absorbed from) theintestinal tract much in the manner of ordinary triglyceride fats oroils, whereas those polyol esters which contain 4 or more ester groupsare generally substantially nondigestible and consequently nonabsorbableby the human body. It is not necessary that all of the hydroxyl groupsof the polyol be esterified, but it is preferable that disaccharidemolecules contain no more than 3 unesterified hydroxyl groups, and morepreferably no more than 2 unesterified hydroxyl groups, so that they arerendered nondigestible. Typically, substantially all (e.g., at leastabout 85%) of the hydroxyl groups of the polyol are esterified,preferably at least about 95% of the hydroxyl groups of the polyol areesterified. In the case of sucrose polyesters, typically from about 7 to8 of the hydroxyl groups of the polyol are esterified.

In one preferred composition, the solid polyol fatty acid polyestercomprises (i) a solid saturated polyol polyester, and (ii) a soliddiversely esterified polyol polyester, the ratio of (i):(ii) being fromabout 1:20 to about 4:1.

i) Solid Saturated Polyol Polyester

The solid saturated polyol polyester comprises esters of essentiallyonly, and preferably only, long chain saturated fatty acid radicalswhich are typically normal and contain at least 14, preferably 14 to 26,and more preferably 16 to 24, and most preferably from 20 to 24, carbonatoms. Particularly preferred are saturated fatty acid radicals of 22carbon atoms. The long chained saturated radicals can be used incombination with each other in all proportions. The average degree ofesterification of these solid saturated polyol polyesters is such thatat least 4 of the hydroxyl groups of the polyol are esterified. In thecase of sucrose polysaturate esters, from about 7 to 8 of the hydroxylgroups of the polyol are preferably esterified. Typically, substantiallyall (e.g., at least about 85% preferably at least about 95%) of thehydroxyl groups of the polyol are esterified.

Examples of suitable long chain saturated fatty acid radicals includetetradecanoate (myristate), hexadecanoate (palmitate), octadecanoate(stearate), elcosanoate (arachidate), docosanoate (behenate),tetracosanate (lignocerate), and hexacosanoate (cerotate). Mixed fattyacid radicals from completely or substantially completely hydrogenatedvegetable oils which contain substantial amounts of the desired longchain saturated fatty acids can be used as sources of fatty acidradicals in preparing the solid polyol polyesters useful in the presentinvention. The mixed fatty acids from such oils should preferablycontain at least about 30% (more preferably at least about 50%, mostpreferably at least about 80%) of the desired long chain saturated fattyacids. Suitable source oils include completely or substantiallycompletely hydrogenated soybean oil, cottonseed oil, palm oil, peanutoil, corn oil, safflower oil, sunflower oil, sesame oil, low erucic acidrapeseed oil (i.e. canola oil), and high erucic acid rapeseed oil. Theseoils are typically hydrogenated to an Iodine Value of about 12 or less,and preferably to an Iodine Value of about 8 or less.

Examples of solid polyol polyesters useful as hardstocks in the fatcompositions of the present invention include sucrose octabehenate,sucrose octastearate, sucrose octapalmitate, sucrose heptastearate,xylitol, pentastearate, galactose pentapalmitate, and the sucrose hepta-and octaesters of soybean oil and high erucic acid rapeseed oil fattyacids that have been hydrogenated to an Iodine Value of about 8 or less.

The solid saturated polyol polyester generally by itself crystallizesinto well defined spherulitic particles from a molten composition at orbelow the onset crystallization temperature of the solid saturatedpolyol polyester. The onset crystallization temperature is thattemperature at which a solid polyol fatty acid polyester can first beginto crystallize in the liquid polyol fatty acid polyester. That is, whendissolved in a molten composition comprising the solid saturated polyolpolyester in a liquid polyol fatty acid polyester, the solid saturatedpolyol polyester will tend to form well defined, highly ordered,substantially sphere-shaped crystals, called spherulites, when permittedto cool and crystallize at a first crystallization temperature. In theabsence of other solid nondigestible oil components, such as a soliddiversely esterified polyol polyester or a polyol polyester polymer, thesolid saturated polyol polyester would normally crystallize intospherical-shaped particles called spherulites having a diameter (ormaximum particle dimension) of about 3 microns or larger, usually about3-32 microns, the size being a function of the initial concentration ofthe solid saturated polyol polyester in the liquid polyol fatty acidpolyester and the rate of shearing applied during the crystallization.As will be understood from the processing description herein after, ifrapidly cooled and crystallized under shear, a solid saturated polyolpolyester will tend to crystallize as discrete non-spherulite particles,typically of less than about 30 microns, preferably less than about 10microns (although portion of the crystals can form as very smallspherulites may also form), as opposed to the above mentioned largerspherulites which readily form at slower rates of cooling(crystallizing) and slower rates of shear.

When co-crystallized with other solid polyol fatty acid polyestercomponents, such as the solid diversely esterified polyol polyesters orpolyol polyester polymers, the solid saturated polyol polyester willtend not to form the highly ordered spherulite particles.

ii) Solid Diversely Esterified Polyol Polyesters

The solid diversely esterified polyol polyester of the present inventioncomprises polyol polyesters which have their ester group-forming fattyacid radicals selected so that the polyol backbone does not contain allof a single type of ester group. Generally, these polyol polyesterscontain two basic types of ester groups. These are (a) ester groupsformed from long chain saturated fatty acid radicals, as herein abovedescribed, and (b) dissimilar ester groups formed from acid radicalswhich are “dissimilar” to the long chain saturated fatty acid radicals.When these “dissimilar” fatty acid and/or other organic acid radicalsare esterified onto a polyol that contains or will contain long chainsaturated fatty acid radicals, they will introduce diverseesterification into the resulting polyol polyester molecule, therebyaltering the crystal structure as these molecules pack together duringcrystallization. This diverse esterification can be due to differencesin length of the ester forming acid radicals (e.g., short chain versuslong chain), or other steric factors, e.g. branched chain versusstraight chain, unsaturated chain versus saturated chain, aromatic chainversus aliphatic chain, etc. Polyol polyesters containing these “longchain” and “dissimilar” ester groups are therefore herein called “soliddiversely esterified polyol polyesters”.

The solid diversely esterified polyol polyesters tend to have“asymmetrical” or irregular molecular structures. It is believed thatthe asymmetrical structure of these molecules interfere with the normalpacking tendency of the symmetrical solid saturated polyol polyestermolecules during co-crystallization in the liquid polyol polyester. Thisinterference blocks the usual unrestrained three dimensional growth ofthe solid saturated polyol polyester molecules and thus inducesrestrained three dimensional growth or otherwise induces growth in atmost two dimensions, e.g., the formation of relatively thinplatelet-like particles.

The dissimilar ester groups are formed from acid radicals selected fromlong chain unsaturated fatty acid radical, short chain saturated fattyacid radical, and other dissimilar fatty acid radicals, and mixturesthereof. The preferred dissimilar acid radical is a long chainunsaturated fatty acid radical.

The long chain unsaturated fatty acid radicals are typically straightchain (i.e., normal) mono- and di-unsaturates, and contain at leastabout 12, preferably about 12 to about 26, more preferably about 18 to22, and most preferably 18 carbon atoms. Examples of suitable long chainunsaturated fatty acid radicals for the solid polyol polyesters hereinare lauroleate, myristoleate, palmitoleate, oleate, elaidate, erucate,linoleate, linolenate, arachidonate, eicosapentaenoate, anddocosahexaenoate. For oxidative stability, the mono and/or diunsaturatedfatty acid radicals are preferred.

The short chain saturated fatty acid radicals are typically normal andcontain 2 to 12, preferably 6 to 12 and most preferably 8 to 12, carbonatoms. Examples of suitable short chain saturated fatty acid radicalsare acetate, butyrate, hexanoate (caproate), octanoate (caprylate),decanoate (caprate), and dodecanoate (laurate).

Other dissimilar ester-forming radicals can include fatty-fatty acidradicals having at least one hydroxyl group that is esterified withanother fatty or other organic acid. Nonlimiting examples of suitablefatty-fatty acid radicals include 12-hydroxy-9-octadecenoic acid(ricinoleic acid), 12-hydroxy-octadecanoic acid, 9-hydroxy-octadecanoicacid, 9-hydroxy-10, 12-octadecadienoic acid, 9-hydroxy-octadecanoic, 9,10-dihydroxyoctadecanoic acid, 12, 12-dihydroxyeicosanoic acid, and18-hydroxy-9, 11, 13-octadecatrienoic acid (kamolenic acid). Ricinoleicacid is a preferred hydroxy-fatty acid. Castor oil is a convenientsource of ricinoleic acid. Other sources of hydroxy-fatty acids includehydrogenated castor oil, strophanthus seed oils, calendula officinalisseed oils, hydrogenated strophanthus seed oils and hydrogenatedcalendula officinalis seed oils, cardamine impatiens seed oils, kamalaoils, mallotus discolor oils, and mallotus claoxyloides oils.

Specific, non-limiting examples of solid polyol fatty acid polyesters ofthe present invention are sorbitol hexaester in which the acid esterradicals are palmitoleate and arachidate in a 1:2 molar ratio; theoctaester of raffinose in which the acid ester radicals are linoleateand behenate in a 1:3 molar ratio; the heptaester of maltose wherein theesterifying acid radicals are sunflower seed oil fatty acids andlignocerate in a 3:4 molar ratio; the octaester of sucrose wherein theesterifying acid radicals are oleate and behenate in a 2:6 molar ratio;and the octaester of sucrose wherein the esterifying acid radicals arelaurate, linoleate and behenate in a 1:3:4 molar ratio. A preferredmaterial is sucrose polyester in which the degree of esterification is7-8, and in which the fatty acid radicals are C₁₈ mono- and di-unsaturated and behenic, in a molar ratio of about 2:6 to about 1.5:6.5.

iii) Solid Polyol Polyester Polymers

Polyol polyester polymers are those formed by polymerizing a polyolpolyester monomer to provide a molecule having at least two separateesterified polyol moieties linked by covalent bonds between ester groupsof these different polyol moieties. For example, two sucroseoctabehenate monomers could be cross-linked between fatty acids to forma polymer. Repeating units of such polyol polyester polymers can be thesame or different such that the generic term “polymer” in this contextincludes the specific term “copolymer”. The number of repeating monomer(or co-monomer) units which make up such polyol polyester polymers canrange from about 2 to 20, preferably from about 2 to 12. Depending onthe method of preparing them, the polyol polyester polymers arefrequently oligimers containing from 2 to 4 monomeric units, i.e., aredimers, trimers, or tetramers. The most typical type of polyol polyesterpolymer for use herein is dimer.

When sucrose is used as the polyol of the polyester polymer, it ispreferably completely esterified with fatty acid or other estergroup-forming acid radicals. Using sucrose as the polyol, completelyesterified sucrose polyester monomer, dimer, and trimer are shownschematically in FIGS. 1a, 1 b, and 1 c, respectively. At least about15%, preferably at least about 45%, more preferably at least about 75%,and most preferably at least about 90% of the hydroxyl groups of thepolyol polyester polymer material should be esterified with long chain(C₂₀ and higher) saturated fatty acid radicals. The sucrose polyesterpolymers used herein can advantageously have a number, average molecularweight of from about 4000 to about 60,000, preferably from about 4000 toabout 36,000, more preferably from about 5000 to about 12,000.

Suitable long chain saturated fatty acid radicals for use in preparingthe polyol polyester polymers (and its monomers) include those hereinbefore described for preparing the solid diversely esterified polyolpolyesters. As in the case of the solid diversely esterified polyolpolyesters, mixed fatty acid radicals from source oils which containsubstantial amounts of the desired long chain saturated fatty acids(i.e, at least about 30%, preferably at least about 50%, more preferablyat least about 80%) can be used as sources of acid radicals in preparingthese polyol polyester polymers.

Suitable polyol polyester material which forms the solid nondigestibleparticles used in the fat compositions herein will generally comprisefrom about 0% to 99% of the polyol polyester polymer component and from1% to about 100% of the unpolymerized polyol polyester monomercomponent, preferably from about 0% to about 90% of the polyol polyesterpolymer component and from about 10% to about 100% of the monomercomponent, more preferably from about 0% to 70% of the polymer componentand from 30% to about 100% of the monomer component, and most preferablyfrom about 0% to 50% of the polymer component and from 50% to about 100%of the monomer component.

2. Processes for Making Solid Polyol Fatty Acid Polyesters

The solid polyol fatty acid polyesters, including the solid saturatedpolyol polyester and the solid diversely esterified polyol polyester,the solid polyol polyester polymer and the solid polyol polyesterpolymer, used in the present invention can be made according to priorknown methods for preparing polyesters of polyols. Since the sucrosepolyesters are the preferred solid polyol polyesters herein, theinvention will be exemplified primarily by these materials.

One such method of preparation is by reacting the acid chlorides of thefatty acids with sucrose. In this method a mixture of the acid chlorideor acid anhydrides of the fatty acids can be reacted in one step withsucrose, or the acid chlorides can be reacted sequentially with sucrose.Another preparation method is by the process of reacting methyl estersof the fatty acids with sucrose in the presence of a fatty acid soap anda basic catalyst such as potassium carbonate. See, for example, U.S.Pat. Nos. 3,963,699, Rizzi et al., issued Jun. 15, 1976; U.S. Pat. No.4,518,772, Volpenhein, issued May 21, 1985; and U.S. Pat. No. 4,517,360,Volpenhein, issued May 14, 1985, and U.S. Ser. No. 417,990, Letton,filed Oct. 6, 1989, all incorporated herein by reference. Methods forpreparing polyol polyester polymers are described in U.S. Pat. No.5,451,416, issued Sep. 19, 1995 (Johnston et. al.) the disclosure ofwhich is incorporated herein by reference.

When using the methyl ester route for preparing the solid polyolpolyesters herein, the fatty acid methyl esters are blended in thedesired ratio and reacted with sucrose by transesterification to obtainthe sucrose esters of mixed unsaturated/saturated or saturated fattyacids. In a preferred way of practicing the methyl ester process, fivemoles of the blended saturated/unsaturated or saturated methyl estersare reacted with sucrose in a first stage at 135° C. to obtain partialesters of sucrose. An additional nine moles of the blended esters arethen added and the reaction continued at 135° C. under reduced pressureuntil the desired degree of esterification has been attained.

When two or more of the solid saturated polyol polyester, soliddiversely esterified polyol polyester and solid polyol polyester polymerare used as the solid polyol polyester, then can be made andincorporated separately into the nondigestible oil composition, oralternatively, they can be made and mixed together and incorporated intothe nondigestible oil composition. In a preferred process where thesolid polyol fatty acid polyester comprises the solid saturated polyolpolyester and the solid diversely esterified polyol polyester, the twosolid polyesters are made simultaneously in the same polyolesterification preparation. The preferred method of making the solidpolyol fatty acid polyester is to esterify the polyol with a mixture oflong chain saturated fatty acid lower alkyl (preferably methyl) esters,and dissimilar fatty acid alkyl (preferably methyl) esters selected fromshort chain saturated fatty acid alkyl esters, long chain unsaturatedfatty acid alkyl esters, dissimilar acid alkyl esters, and mixturesthereof. When prepared in the same preparation, the esterification ofthe polyol hydroxy sites by the mixture of long chain saturated fattyacid radicals and dissimilar fatty acid radicals will occursubstantially randomly. In order to ensure that a portion of the solidpolyol polyesters are esterified only with long chain saturated fattyacid radicals, it is generally required to include proportionally moreof the long chain saturated fatty acid radicals as compared to thedissimilar fatty acid radicals. For example, sucrose has 8 hydroxy siteswhich are capable of being esterified. Depending upon the chain lengthsof the esters and other processing conditions, in order to obtain asignificant (10% or greater) amount of sucrose octasaturate and sucroseheptasaturate polyester from the reaction of sucrose with a mixture oflong chain saturated fatty acid methyl esters and long chain unsaturatedfatty acid methyl esters, a molar ratio of long chain saturated estersto long chain unsaturated esters of about 6:2 or more will be needed. Asan example of a particularly preferred solid polyol polyester, a molarratio of 6.5:1.5 of C22 saturated fatty acid ester to cottonseed oil(about 73% unsaturated) ester is used, resulting in about 20% on a molarbasis of sucrose octasaturate and sucrose heptasaturate polyester (asthe solid saturated polyol polyester), with the remaining polyesters(about 80% on a molar basis) being substantially octa- andhepta-substituted and having a mixture of long chain saturated fattyacid radicals and long chain unsaturated fatty acid radicals (as thediversely esterified polyol polyester). Increasing the ratio of longchain saturated radicals to long chain unsaturated radicals will resultin a higher proportion of the solid polyesters being converted to solidsaturated polyol polyesters; conversely decreasing the ratio of longchain saturated fatty acid radicals to long chain unsaturated fatty acidradicals will tend to result in a lower proportion of the solidpolyesters being converted to the solid saturated polyol polyesters.

Mixed fatty acid radicals from source oils which contain substantialamount of the desired unsaturated or saturated acids can be used as thefatty acid radicals to prepare compounds of the invention. The mixedfatty acid radicals from the oils should contain at least about 30%(preferably at least about 50%, most preferably at least about 80%) ofthe desired unsaturated or saturated acids. For example, rapeseed oilfatty acid radicals or soybean oil fatty acid radicals can be usedinstead of pure C₁₂-C₂₆ unsaturated fatty acids. Hardened (i.e.,hydrogenated) high erucic rapeseed oil fatty acids can be used insteadof pure C₂₀-C₂₆ saturated fatty acids. Preferably the C₂₀ and higheracids (or their derivatives—e.g., methyl esters) are concentrated, forexample by distillation. The fatty acids from palm kernel oil or coconutoil can be used as a source of C₈ to C₁₂ acids. An example of the use ofsource oils to make solid polyol polyesters of the invention is thepreparation of solid sucrose polyester, employing the fatty acids ofhigh oleic sunflower oil and substantially completely hydrogenated higherucic rapeseed oil. When sucrose is substantially completely esterifiedwith a 1:3 by weight blend of the methyl esters of the fatty acids ofthese two oils, the resulting sucrose polyester will have a molar ratioof unsaturated C₁₈ acid radicals to C₂₀ and higher saturated acidradicals of about 1:1 and 28.6 weight percent of the total fatty acidsin the polyester will be C₂₀ and C₂₂ fatty acids. The higher theproportions of the desired unsaturated and saturated acids in the fattyacid stocks used in making the solid polyol polyester, the moreefficient the ester will be in its ability to bind liquid oils.

One way to prepare this material is by synthesizing monomeric polyolpolyester according to known polyol esterification, transesterificationand/or interesterification methods and by then polyrmerizing thesemonomers. The polymerization step can be initiated and promoted by anyof a number of well known methods, including, but not limited to,photochemical reactions and reactions with transition metal ions, heator free radical initiators such as di-tert-butyl peroxide.

Alternatively, polyol polyester polymers can be prepared directly byesterifying and/or interesterifying the polyol material with polybasicpolymerized fatty acids or their derivatives. For example, the polyolpolyester polymers could be prepared by reacting the acid chlorides oracid anhydrides of the desired esterifying polymer acids with sucrose,preferably using a sequential esterification process in the mannerdescribed herein before for the preparation of diversely esterifiedpolyol polyesters. The polyol polyester polymers could also be preparedby reacting the methyl esters of the desired polymer acids with sucrosein the presence of a fatty acid soap and a basic catalyst, such aspotassium carbonate in the manner described herein before for thepreparation of diversely esterified polyol polyesters.

When using the foregoing methods for preparing sucrose polyestermaterial containing both unpolymerized and polymerized fatty acidgroups, the molar ratio of unpolymerized to polymerized fatty acids inthe resulting sucrose material can range from about 2:6 to about 4:4.

When using the acid chloride or methyl ester procedures herein beforedescribed to esterify the polyol with already polymerized fatty acids, awide variety of pre-polymerized fatty acid materials can be used. Onesuch class of suitable polymerized fatty acids comprises long-chain,aliphatic, dibasic acids having from about 28 to about 44 carbon atomsin their molecules. They are generally formed from unsaturated fattyacids having from about 14 to about 22 carbon atoms which can bepolymerized. For example linoleic acid can be polymerized by heating toform linoleic acid dimer as follows:

Common examples of polymerizable acids of this type are those containingtwo or more double bonds (polyunsaturated acids) such as theoctadecadienoic acids containing two double bonds, for example, theabove-mentioned linoleic acid, and the octadecatrienoic acids containing3 double bonds, for example, linolenic and eleostearic acids. Othercommon polymerizable polyunsaturated acids having from about 14 to about22 carbon which can be used to esterify polyols and thereby form thepolyol polyester polymers herein are octadecatrienoic acid (e.g.,licanic acid), actadectetraenoic acid (e.g., parinaric acid),eicosadienoic acid, eicostetraenoic acid (e.g., arachidonic acid),5,13-docosadienoic acid and clupanodonic acid. Monounsaturated fattyacids, such as oleic, elaidic and erucic acids, can also be used inpreparing suitable long chain fatty acid dimers which in turn can thenbe used to form the solid polyol polyester polymer particles used in thepresent invention.

Mixed fatty acid radicals from source oils which contain substantialamounts of the desired polymerizable polyunsaturated or monounsaturatedfatty acids can be used as sources of acid radicals in preparing thepolyol polyester polymer materials used to form the solid particles usedin the present invention. The mixed fatty acids from such source oilsshould preferably contain at least about 30% (more preferably at leastabout 50%, most preferably at least about 80%) of the desiredpolymerizable polyunsaturated or monounsaturated fatty acids.

Illustrative of natural sources which are rich in linoleic acid aresoybean oil, cottonseed oil, peanut oil, corn oil, sesame seed oil,sunflower seed oil, safflower oil, linseed oil and perrilla oil.Oiticica oil is a particularly good source of licanic acid and tung oilcontains a high concentration of eleostearic acid. Fish oils, such asherring, menhaden, pilchard, salmon and sardine oil are also suitablesources of polymerizable acids, particularly the higher fatty acids suchas arachidonic and clupanodonic acids. Other oils such as tall oil,dehydrated castor oil, olive oil and rapeseed oil also containsignificant proportions of suitable unsaturated acids. For example,olive oil is rich in oleic acid and rapeseed oil is rich in erucic acid.

Preferred polybasic polymerized fatty acids and fatty acid derivativesfor use in preparing polymer-containing polyol polyesters includedibasic acids produced by dimerization of the fatty acids or fatty acidlower esters derived from polyunsaturated vegetable oils such as soybeanoil or cottonseed oil or from animal fats such as tallow.

All of the foregoing types of polybasic polymerized fatty acids maythemselves be made by a variety of methods known to those skilled in theart. (See Lutton; U.S. Pat. No. 3,353,967; Issued Nov. 21, 1967, Goebel;U.S. Pat. No. 2,1482,761; Issued Sep. 27, 1949, Harrison et al; U.S.Pat. No. 2,731,481; Issued Jan. 17, 1956 and Barrett et al; U.S. Pat.No. 2,793,219; Issued May 21, 1957, all of which are incorporated hereinby reference.)

As noted, a mixture of both polymerized and unpolymerized polyolpolyester material can be prepared by reacting the polyol with bothpolymerized and unpolymerized esterifying fatty acids or fatty acidderivatives. In a preferred method for preparing particularly desirablesolid sucrose polyester material comprising sucrose polyester polymers,fractionated or unfractionated high erucic acid rapeseed (HEAR) methylesters are partially polymerized, hardened and then reacted withsucrose. Another method of making these especially desirable solidsucrose polyesters is to make liquid sucrose polyester materialesterified with fatty acid groups of high erucic acid rapeseed oil by aconventional process, to then partially polymerize the resulting liquidsucrose polyester material, and to then harden the resulting polymerizedmaterial.

3. Liquid Polyol Fatty Acid Polyester

A key component of the nondigestible oil composition herein is a liquidpolyol fatty acid polyester having a complete melting point below about37° C. Suitable liquid nondigestible edible oils for use herein includeliquid polyol polyesters (see Jandacek; U.S. Pat. No. 4,005,195; issuedJan. 25, 1977); liquid esters of tricarballylic acids (see Hamm; U.S.Pat. No. 4,508,746; issued Apr. 2, 1985); liquid diesters ofdicarboxylic acids such as derivatives of malonic and succinic acid (seeFulcher, U.S. Pat. No. 4,582,927; issued Apr. 15, 1986); liquidtriglycerides of alpha-branched chain carboxylic acids (see Whyte; U.S.Pat. No. 3,579,548; issued May 18, 1971); liquid ethers and ether esterscontaining the neopentyl moiety (see Minich; U.S. Pat. No. 2,962,419;issued Nov. 9, 1960); liquid fatty polyethers of polyglycerol (SeeHunter et al; U.S. Pat. No. 3,932,532; issued Jan. 13, 1976); liquidalkyl glycoside fatty acid polyesters (see Meyer et al; U.S. Pat. No.4,840,815; issued Jun. 20, 1989); liquid polyesters of two ether linkedhydroxypolycarboxylic acids (e.g., citric or isocitric acid) (see Huhnet al; U.S. Pat. No. 4,888,195; issued Dec. 19, 1988); and liquid estersof epoxide-extended polyols (see White et al; U.S. Pat. No. 4,861,613;issued Aug. 29. 1989); as well as liquid polydimethyl siloxanes (e.g.Fluid Silicones available from Dow Corning). All of the foregoingpatents relating to the liquid nondigestible oil component areincorporated herein by reference.

Preferred liquid nondigestible oils are the liquid polyol polyestersthat comprise liquid sugar polyesters, liquid sugar alcohol polyesters,and mixtures thereof. The preferred sugars and sugar alcohols forpreparing these liquid polyol polyesters include erythritol, xylitol,sorbitol, and glucose, with sucrose being especially preferred. Thesugar or sugar alcohol starting materials for these liquid polyolpolyesters are preferably esterified with fatty acids containing from 8to 22 carbon atoms, and most preferably from 8 to 18 carbon atoms.Suitable naturally occurring sources of such fatty acids include cornoil fatty acids, cottonseed oil fatty acids, peanut oil fatty acids,soybean oil fatty acids, canola oil fatty acids (i.e. fatty acidsderived from low erucic acid rapeseed oil), sunflower seed oil fattyacids, sesame seed oil fatty acids, safflower oil fatty acids,fractionated palm oil fatty acids, palm kernel oil fatty acids, coconutoil fatty acids, tallow fatty acids and lard fatty acids.

The nondigestible polyol polyesters that are liquid are those which haveminimal or no solids at body temperatures (i.e., 98.6° F., 37° C.).These liquid polyol polyesters typically contain ester groups having ahigh proportion of C₁₂ or lower fatty acid radicals or else a highproportion of C₁₈ or higher unsaturated fatty acid radicals. In the caseof those liquid polyol polyesters having high proportions of unsaturatedC₁₈ or higher fatty acid radicals, at least about half of the fattyacids incorporated into the polyester molecule are typicallyunsaturated. Preferred unsaturated fatty acids in such liquid polyolpolyesters are oleic acid, linoleic acid, and mixtures thereof.

The following are nonlimiting examples of specific liquid polyolpolyesters suitable for use in the present invention: sucrosetetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucroseheptaoleate, sucrose octaoleate, sucrose hepta- and octaesters ofunsaturated soybean oil fatty acids, canola oil fatty acids, cottonseedoil fatty acids, corn oil fatty acids, peanut oil fatty acids, palmkernel oil fatty acids, or coconut oil fatty acids, glucose tetraoleate,the glucose tetraesters of coconut oil or unsaturated soybean oil fattyacids, the mannose tetraesters of mixed soybean oil fatty acids, thegalactose tetraesters of oleic acid, the arabinose tetraesters oflinoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitoltetraoleate, the sorbitol hexaesters of unsaturated soybean oil fattyacids, xylitol pentaoleate, and mixtures thereof.

The liquid polyol polyesters suitable for use in the compositions hereincan be prepared by a variety of methods known to those skilled in theart. These methods include: transesterification of the polyol (i.e.sugar or sugar alcohol) with methyl, ethyl or glycerol esters containingthe desired acid radicals using a variety of catalysts; acylation of thepolyol with an acid chloride; acylation of the polyol with an acidanhydride; and acylation of the polyol with the desired acid, per se.(See, for example, U.S. Pat. Nos. 2,831,854, 3,600,186, 3,963,699,4,517,360 and 4,518,772, all of which are incorporated by reference.These patents all disclose suitable methods for preparing polyolpolyesters.)

4. Other Shortening Ingredients

So long as they do not interfere with the formation of the flowablenondigestible oil, the flowable nondigestible oil compositions may alsocomprise other shortening ingredients. Various additives can be usedherein provided they are edible and aesthetically desirable and do nothave any detrimental effects on the shortenings. These additives includeedible, digestible oils and hardstock, fat-soluble vitamins, flavoringsand seasonings, emulsifiers, anti-spattering agents, chelating agents,anti-sticking agents, antioxidants, anti-foaming agents (for fryingapplications) or the like.

5. Formation of Stiffened Nondigestible Oil

Ordinarily, and when not practicing the process of the presentinvention, the nondigestible oil composition described herein is capableof crystallizing from a molten liquid form to a stiffened nonflowableoil form when the nondigestible oil composition is rapidly cooled fromthe molten temperature to the crystallization temperature of the solidpolyol polyester, or less (for example, to body temperature, about 37°C.) under substantially quiescent conditions. This stiffened nonflowablenondigestible oil comprises the liquid nondigestible oil portionretained substantially completely within the crystalline matrix ofcrystallized solid polyol fatty acid polyester, thereby providing thedesired passive oil loss control of the nondigestible oil. Thecomposition and method of making of the food composition should beselected to provide the sufficiently rapid cooling of the nondigestibleoil from a molten temperature to a lower temperature substantially inthe absence of shearing of the food composition, such that the solidpolyol fatty acid polyester has crystallized into the desiredcrystalline form which provides the desired passive oil loss control.Generally, this cooling rate from the onset crystallization temperatureof the highest melting solid polyol fatty acid polyester to thecrystallization temperature (of the lowest melting solid polyol fattyacid polyester component) is greater than about 0.5° C./min, morepreferably greater than about 2.5° C./min, and most preferably greaterthan 25° C./min. In the case of a polyol polyester polymer, which canform the desired crystal structure for passive oil loss control at muchslower cooling rates, a cooling rate of greater than about 0.03° C./min.under the quiescent conditions is generally sufficient to form thedesired crystal structure.

When a nondigestible oil composition comprising a solid polyol fattyacid polyester containing any one or a combination of a solid saturatedpolyol polyester, a solid diversely esterified polyol polyester, and apolyol polyester polymer, begin to crystallize (or co-crystallize) inthe liquid polyol polyester, the crystals (or co-crystals) initiallyappear as discrete, unaggregated entities, suspended in the liquidpolyol fatty acid polyester. Under quiescent cooling conditions, such aswhen the molten nondigestible oil has been processed into food productsvia baking or frying, these discrete unaggregated entities can grow ascrystallization continues, and begin to cluster together to form smallaggregates of at least 3 microns, dispersed in the liquid nondigestibleoil. These small aggregate clusters of particles can develop in avariety of forms and shapes, including spherical, platelet-like,filament-like or rod-like, or combinations of these various shapes, butare typically spherical or platelet-like. Thinner aggregate particles,referred to as platelets, are preferred from the standpoint of providingmore efficient passive oil loss control of the liquid polyol polyestercomponent of the nondigestible oil compositions herein. These plateletparticles preferably have a thickness of about 0.1 micron or less, morepreferably about 0.05 micron or less. As the crystallization continues,the platelets continue to grow and to cluster together to form a largeraggregate particle that is porous in character and thus capable ofentrapping significant amounts of the liquid polyol polyester. It isbelieved that this porous structure and its concomitant ability toentrap large amounts of liquid polyol polyester is why these largeraggregated, platelet-like particles can provide very effective andefficient passive oil loss control, and results in a stiffened,nonflowable nondigestible oil.

B. Process for Making a Flowable Nondigestible Oil Composition

The present invention also provides a process for making a flowablenondigestible oil, wherein the nondigestible oil comprises a) a liquidpolyol fatty acid polyester having a complete melt point less than 37°C., and b) a solid polyol fatty acid polyester having a complete meltpoint of at least about 37° C. The process comprises the steps ofmelting completely the nondigestible oil composition containing thesolid polyol fatty acid polyester, rapidly cooling the meltednondigestible oil to a crystallization temperature, thereby rapidlycrystallizing at least a substantial portion of the solid polyol fattyacid polyester, and shearing the nondigestible oil composition duringthe step of crystallizing to form the flowable nondigestible oilcomposition. Optionally, following the crystallizing and shearing steps,the process can include the step of tempering the crystallizednondigestible oil composition for a time sufficient to substantiallycompletely crystallize all of the solid polyol fatty acid polyester, thestep of adding a stabilizing amount of a diluent liquid, typically aliquid polyol fatty acid polyester, to the crystallized nondigestibleoil composition, or both steps.

The process of the present invention for making a flowable nondigestibleoil typically requires at least about 5 minutes and generally no morethan about 3 hours, preferably at least about 5 minutes and generally nomore than about 2 hours, more preferably at least about 10 minutes andno more than about 1 hour, and most preferably at least about 15 minutesand no more than about 30 minutes.

Without the invention being bound by any theory of crystallizationdescribed herein, it is understood that crystallization of the solidpolyol fatty acid polyester occurs kinetically. As with any kineticreaction, a dynamic equilibrium can be achieved wherein the reaction mayappear to have halted. Then, by changing the conditions, the reactioncan be made to proceed forward, or even to reverse. In the same way, thesolid polyol fatty acid polyester can crystallize under a conditionuntil a dynamic equilibrium is achieved. The dynamic equilibrium canexist wherein a portion of a solid polyol fatty acid polyester is stilldissolved in the liquid polyol polyester while the preponderance hasbeen crystallized. The rate at which a solid polyol fatty acid polyesterwill crystallize depends upon several factors, such as, the molecularcomposition of the solid polyol fatty acid polyester, the concentrationof the solid polyol fatty acid polyester, the proportion of solid polyolfatty acid polyester already crystallized to that remaining dissolved inthe liquid polyol fatty acid polyester, and the temperature differentialbetween the onset crystallization temperature of the solid polyol fattyacid polyester and the temperature of crystallization. At the onset ofcrystallization, the solid polyol fatty acid polyester will initiallycrystallize at a high crystallization rate. This crystallization rateslows with time, eventually (ideally) to a rate of zero. Then, when thesolution is further cooled to a lower temperature the equilibrium isshifted such that additional solid polyol fatty acid polyester cancrystallize from the liquid polyol polyester. While the proportion ofsolid polyol fatty acid polyester which will crystallize with anincremental reduction in temperature is generally low, it is believedthat additional crystallizing solid polyol fatty acid polyester will, inthe absence of shearing, tend to crystallize as discrete, unaggregatedentities suspended in the liquid polyol fatty acid polyester or ontoother aggregate particles. The discrete unaggregated entities may beginto cluster together to form small aggregates, typically up to severalmicrons in size. However, in the presence of applied shear, theseunaggregated entities generally do not form into aggregate particles,and any aggregate particles that might form do not generally continue tocluster into a large matrix of crystal aggregate, thereby promoting theflowability of the nondigestible oil.

The flowable nondigestible oil composition of the present invention canbe processed using crystallization and mixing equipment that is commonlyemployed to crystallize fats. Both batch and continuous processingsystems and equipment can be used, though a continuous system isgenerally preferred. The general requirement of the system is to becapable of rapidly cooling the molten polyol polyester component to thecrystallization temperature range, and crystallizing at least asubstantial portion of the solid polyol fatty acid polyester, mostpreferably while simultaneously shearing the composition sufficiently toform the flowable nondigestible oil composition.

1. Melting of the Nondigestible Oil Composition

The first step of the process of the present invention comprises meltingthe solid polyol fatty acid polyesters in the liquid polyol polyester ata temperature above the temperature where the last amount of solidmaterial of the solid polyol fatty acid polyester is melted into theliquid. Preferably, the composition is raised to a temperature at least10° C. above the complete melt temperature of the solid polyol fattyacid polyester.

In the molten state, the nondigestible oil compositions are generallytransparent and clear. It will be observed that as solid polyol fattyacid polyester begins to crystallize (at and below the onsetcrystallization temperature of the solid polyol fatty acid polyester),the liquid polyol polyester begins to become turbid and clouded. The“onset crystallization temperature” for a solid polyol fatty acidpolyester can be determined by the method described below in theAnalytical section.

2. Crystallization of the Solid Polyol Fatty Acid Polyester

The next step of the process comprises rapidly crystallizing at least asubstantial portion of the solid polyol fatty acid polyester, defined asat least more than 50% by weight, and preferably more than 80%, morepreferably more than 95%, and most preferably more than 99%. This stepcan comprise the steps of reducing the temperature of the molten polyolpolyester composition to a crystallization temperature of the solidpolyol fatty acid polyester, and holding the polyol polyestercomposition at the crystallization temperature for a time sufficient tocrystallize the substantial portion of the solid polyol fatty acidpolyester. The crystallization temperature is preferably within acrystallization temperature range of from about the onsetcrystallization temperature of the solid polyol fatty acid polyester,down to about 25° C., preferably down to about 10° C. Where the solidpolyol fatty acid polyester contains two or more distinct solid polyolfatty acid polyester materials having different onset meltingtemperatures, preferably the crystallization temperature is below thelowest onset temperature thereof, and preferably at least about 5° C.,more preferably at least about 10° C., below the lowest onsetcrystallization temperature. Most preferably, the crystallizationtemperature of the solid polyol fatty acid polyester is within thetemperature range of the storage conditions for the flowablenondigestible oil, typically about 15° C. to about 40° C. though morepreferably about 25° C. to about 30° C. It should be understood that therate of crystallization of the solid polyol fatty acid polyester will behigher as the crystallization temperature is reduced lower below theonset crystallization temperature of the solid polyol polyester.

The step of rapidly crystallizing the substantial portion of the solidpolyol fatty acid polyester typically is completed in less than about 30minutes, preferably in less than about 5 minutes, and more preferably inless than about 30 seconds, and most preferably in less than about 15seconds. Generally about 5 seconds to about 30 seconds are neededdepending upon the type of equipment used. While the step can becompleted within a period of time of more than 30 minutes, suchadditional time is understood to provide no particular additionalbenefits.

The process also comprises the step of shearing during the step ofcrystallizing the solid polyol fatty acid polyester at thecrystallization temperature. By applying shear to the composition duringthe crystallization, the solid polyol fatty acid polyester is encouragedto crystallize into discrete crystals and unaggregated crystalplatelets. By shearing while the crystallization is occurring, theresulting discrete and unaggregated crystals can be inhibited fromgrowing to a size that might be large enough to separate from the liquidphase. It is also believed that the small crystal platelets mayaggregate, into small aggregate particles, but that the shearinginhibits the small aggregate particles from further clustering intolarger aggregate particles which can begin to stiffen the composition.During the crystallizing step, shear is imparted to the polyol polyestercomposition at from about 400 sec⁻¹ to about 8000 sec⁻¹, more preferablyat from about 500 sec⁻¹ to about 6000 sec⁻¹.

The crystallizing step can be conducted in such equipment as aswept-wall, scraped-wall, or screw-type heat exchanger or equivalent,scraped wall agitated reactors, plate and frame heat exchangers, andtube and shell heat exchangers. Such equipment in general cools thecomposition at a rate of from about 0.4° C./min. to 300° C./min., morepreferably from about 0.8° C./min. to about 150° C./min. Examples ofsuch heat exchangers include Cherry Burrell Votator, Girdler “A” units,a Sollich Turbo Temperer, and a Groen Model #DR(C) used for margarineand shortening manufacture, and Aasted chocolate tempering units. Apreferred unit is the Votator unit which consists of a steel shaftrotating in a tube which is cooled externally by a coolant. The rotatingshaft is fitted with scraper blades which press against the cool innersurface at high rotation speeds, continuously scraping the crystallizingcomposition from the inner surface of the tube. References to theseconventional units include: Greenwell, B. A., J. Amer. Oil Chem. Soc.,March 1981, pp. 206-7; Haighton, A. J., J. Amer. Oil Chem. Soc., 1976,Vol. 53, pp. 397-9; Wiedermann, L. H. J. Amer. Oil Chem. Soc., Vol. 55,pp. 826-7; Beckett, S. T., editor, Industrial Chocolate Manufacture andUse, Van Nostrand Reinhold, New York, 1988, pp. 185-9. All of thesepublications are incorporated herein by reference.

A scraped wall heat exchanger is a preferred apparatus for rapidlyreducing the temperature and crystallizing the composition under highshear, typically at temperature reduction rates of about 8-300° C./min.,and preferably about 100-300° C./min. The temperature of the coolantused for this crystallizing step in this equipment is sufficiently lowto quickly cool the polyol polyester composition, but not so low so asto cause a significant amount of plating out of the polyol polyesteronto the chilled surfaces of the apparatus. Typically the coolanttemperature is in the range of from about −23° C. to about 20° C., morepreferably in the range of from about −6.7° C. to about 7° C. Typicalcoolants include liquid ammonia, brine, and other refrigerants.

The melted oil can also be pre-cooled before entering the scraped wallheat exchanger, to a temperature not far above the onset crystallizationtemperature of the solid polyol fatty acid polyester, using a separateheat exchanger.

In general, the rate of shearing to be applied of the composition duringthe crystallization step should be commensurate with the rate ofcrystallization of the solid polyol polyester. That is, for example,when the crystallization temperature is set well below the onsetcrystallization temperature such that the rate of crystallization isvery high; then higher rates of shearing are needed to form the desiredcrystal platelet particles. Of course, if the crystallization rategreatly exceeds the shearing rate, such that large aggregate particlesare formed in the composition, the shearing can be continued aftercrystallization has slowed or stopped to effect a reduction in the largeaggregate particles and a resulting more flowable composition, by thebreaking and tearing of the large aggregate particles by the force ofshear.

Following the step of rapidly crystallizing and shearing the polyolpolyester composition to form the discrete and unaggregated crystalparticles, it is preferred to continue shearing the crystallizedcomposition at the crystallization temperature for a time sufficient forcrystallization of the solid polyol fatty acid polyester to comesubstantially to completion, and to allow the solid polyol fatty acidpolyester to complete crystallization to the discrete and unaggregatedcrystal particles. The continued shearing step serves to disrupt theformation of larger aggregate particles and any three-dimensionalcrystalline matrix that otherwise can form from the larger aggregateparticles in the absence of the shearing. Such continued shearingpreferably avoids creating any dead zones in the mixing vessel whichmight resulting in a localized stiffened composition. Typically thecontinued shearing is done for at least about 2 seconds, preferably forabout 5 minutes, and more preferably for at least about 10 minutes.Generally no more than about 2 hours, preferably about no more than 1hour, more preferably no more than about 30 minutes, is required for thecontinued shearing step.

In the continued shearing step, generally less shear is needed incomparison with that used during the crystallization step. Generallyduring the continued shearing step, shear rates range from about 10sec⁻¹ to about 8000 sec⁻¹. Preferred types of apparatus for carrying outthe continued shearing step include any agitated, jacketed vesselcapable of being operated such that preferably air can be excluded fromincorporation into the polyol polyester composition, and the temperatureof the composition can be suitably controlled. An example of a suitablescraped-wall, jacketed, open tank mixer is a Krueter temper kettle(Becken, pp. 183-4). In addition, it is possible to carry out theconditioning step in two or more separate pieces of agitated, heatexchanger equipment. Another mechanical devices that can be used for thecontinued shearing of the crystallized polyol polyester is a Ross 410X-3 or a Readco twin screw mixer.

The continued shearing step can also be accomplished usingnon-mechanical mixing devices such as static mixers, consisting of apipe section having a plurality of mixing elements contained in a seriestherein. Turbulence and shear are imparted to the product as it passesthrough stationary mixing blades within the pipe. Manufacturers ofinline static mixer include Komax and Lightnin.

It is also possible to carry out both the crystallizing step and anycontinued shearing step in a single piece of equipment, such as, forexample, in a turbo temperer such as a Sollich Turbo Tempering column.

3. Tempering

The process of the present invention can optionally include a temperingstep. The tempering step comprises reducing the temperature of thecrystallized polyol polyester composition to a tempering temperaturethat is less than the intended minimum handling and storage temperatureof the flowable nondigestible oil, and holding the composition at thetempering temperature for a time sufficient for any solid polyol fattyacid polyester to substantially complete crystallizing. A tempering stepcan advantageously be employed when the crystallization temperature ofthe crystallizing step is above the intended storage temperature of theflowable nondigestible oil composition. The tempering step is usuallynot required when the crystallization temperature is itself below theintended storage temperature. The tempering temperature is preferably atleast 5° C., more preferably at least 10° C., below the intended ambienthandling/storage temperature of the flowable nondigestible oil.Typically, the tempering temperature is from about 5° C. to about 25°C., preferably about 5° C. to about 15° C.

In order to prevent the aggregation of crystallized particles during thetempering step, shear mixing should be applied to the polyol polyestercomposition. In general the tempering step will take from about 2minutes to about 2 hours, preferably from about 2 minutes to about 1hour, more preferably about 5 minutes to about 20 minutes. The amount ofshearing that is typically provided in the tempering step will besubstantial the same as that provided during the conditioning step,though preferably it is at least about 1 sec⁻¹, and preferably about 25sec⁻¹ to about 50 sec⁻¹. As with the continued shearing, the temperingstep should avoid creating any dead zones in the mixing vessel whichmight result in a localized stiffened composition.

Following the tempering step, the flowable polyol polyester compositionis preferably raised in temperature to the ambient handling/storagetemperature.

4. Diluent Addition

The process of the present invention can also optionally include a stepof adding an amount of, and preferably a stabilizing amount of, adiluent liquid to the crystallized polyol polyester composition in orderto form, and preferably to ensure the stability of, the flowablenondigestible oil. The principle of adding a diluent liquid is toincrease incrementally the solubility of the solid polyol fatty acidpolyester into the liquid polyol polyester, thereby promoting a moreflowable composition. Preferably the diluent liquid is added after thecrystallization temperature has been reduced to the ambient storagetemperature, even more preferably after any tempering step. The additionof the diluent can reduce, and preferably stop, the driving force forsolid polyol polyester in the liquid polyol polyester to crystallize outof solution, and can even result in some amount of resolubilizing ofcrystallized solid polyol polyester back into the liquid phase. Thediluent is added in an amount, relative to the amount of the processednondigestible oil, generally at about 10:1 to about 0.01:1, preferablyabout 2:1 to about 0.01:1, more preferably about 1:1 to about 0.05:1,and most preferably about 0.5:1 to about 0.1:1. The temperature of thediluent liquid at which it is added to the flowable nondigestible oil isfrom about 5° C. to about 50° C., more preferably about 10° C. to about25° C. The temperature of the diluent liquid will depend upon the amountof diluent liquid used, the preferred storage temperature of theflowable nondigestible oil, and other factors that will be understood byone skilled in the art. A preferred diluent is the liquid polyol fattyacid polyester. Other diluents can be other edible oils, preferablynondigestible oils, which are miscible with the liquid polyol polyesterof the flowable nondigestible composition, and are generally lipophilic.

If the flowable nondigestible oil composition is permitted to setwithout any circulation or stirring for an extended period of time, itis possible that minor temperature fluctuations could result in anincremental crystallization of remaining solid polyol polyester in theliquid polyol polyester, which could result in a thickening andstiffening of the composition. Application of additional shear,therefore, would serve to break up any larger aggregate particles thatmay have formed from the clustering of small aggregate particles,thereby reducing the Consistency of the composition.

The step of adding the diluent liquid to the crystallized polyolpolyester composition can be before any continued shearing of thecrystallized composition, or after any continued shearing step. Theadding of the diluent liquid before the continued shearing step reducesthe time needed for the continued shearing.

C. Temperature Sensitive Food Additives

The flowable nondigestible oil composition can further comprisetemperature-sensitive food additives, including fat-soluble and othervitamins, flavorings, and seasonings. The food additives can be addedeither as a particulate or as a liquid. When adding as a particulate,the particulate food additive can be added to the final flowablenondigestible oil, or added during the crystallization of thecompositions at a step where the temperature does not adversely effectthe efficacy of the additive.

The present flowable nondigestible oil compositions can also befortified with vitamins and minerals, particularly the fat-solublevitamins. The fat-soluble vitamins include vitamin A, vitamin D, vitaminK, and vitamin E. (See U.S. Pat. No. 4,034,083 (Mattson) issued Jul. 5,1977, incorporated by reference herein.)

D. Uses of the Nondigestible Oil Compositions

The nondigestible oils, which can be processed into the flowablenondigestible oils of the present invention, can be used in fryingapplications such as the preparation of French fried potatoes, potatochips, corn chips, tortilla chips, chicken, fish, and battered and friedfoods (e.g. shrimp tempura). Preferably, the compositions can be used asshortenings, cooking oils, frying oils, salad oils, and popcorn oils.The compositions may also be used in cooking sprays, margarines andspreads. The individual composition components may be mixed beforepreparing foods or they can be added separately to the foods.

The nondigestible oils can also be used in the production of baked goodsin any form, such as mixes, shelf-stable baked goods, and frozen bakedgoods. Possible applications include, but are not limited to, cakes,brownies, muffins, bar cookies, wafers, biscuits, pastries, pies, piecrusts, granola bars, and cookies, including sandwich cookies andchocolate chip cookies, particularly the storage-stable dual-texturedcookies described in U.S. Pat. No. 4,455,333 of Hong & Brabbs. The bakedgoods can contain fruit, cream, or other fillings. Other baked good usesinclude breads and rolls, crackers, pretzels, pancakes, waffles, icecream cones and cups, yeast-raised baked goods, pizzas and pizza crusts,and baked farinaceous snack foods, and other baked salted snacks.

The herein can also be used as a component of the fat portion of manyother foods such as ice cream, frozen desserts, cheese, meats, chocolateconfections, salad dressings, mayonnaise, margarine, spreads, sourcream, yogurt, coffee creamer, extruded snacks, roasted nuts andbeverages, such as milk shakes.

The compositions of the present invention can be used to substitute fromabout 10% to 100% of the fat/oil in foods. When substituting the presentcompositions for fat in foods which contain fat and non-fat ingredients(e.g., starches, sugar, non-fat milk solids, etc.) the solid polyolpolyesters are included to control passive oil loss of the nondigestibleoil when said foods are ingested.

The compositions herein can be used in combination with othernondigestible fats, such as branched chain fatty acid triglycerides,triglycerol ethers, polycarboxylic acid esters, sucrose polyethers,neopentyl alcohol esters, silicone oils/siloxanes, and dicarboxylic acidesters. Other partial fat replacements useful in combination with thematerials herein are medium chain triglycerides, triglycerides made withcombinations of medium and long chain fatty acids (like the onesdescribed in European Application 0322027 (Seiden), published Jun. 28,1989, incorporated herein by reference), highly esterified polyglycerolesters, acetin fats, plant sterol esters, polyoxyethylene esters, jojobaesters, mono/diglycerides of fatty acids, and mono/diglycerides ofshort-chain dibasic acids.

The compositions are particularly useful in combination with particularclasses of food and beverage ingredients. For example, an extra caloriereduction benefit is achieved when the present flowable shortenings areused with noncaloric or reduced calorie sweeteners alone or incombination with bulking agents. Noncaloric or reduced caloriesweeteners include, but are not limited to, aspartame saccharin,alitame, thaumatin, dihydrochalcones, acesulfame and cyclamates.

Bulking or bodying agents are useful in combination with thenondigestible oil compositions herein in many food compositions. Thebulking agents can be nondigestible carbohydrates, for example,polydextrose and cellulose or cellulose derivatives, such ascarboxymethylcellulose, carboxyethylcellulose, hydroxypropylmethylcellulose, hvdroxypropylcellulose, methyl cellulose andmicrocrystalline cellulose. Other suitable bulking agents include gums(hydrocolloids), starches, dextrins, fermented whey, tofu,maltodextrins, polyols, including sugar alcohols, e.g., sorbitol andmannitol, and carbohydrates, e.g., lactose.

Similarly, food and beverage compositions can be made that combine thepresent nondigestible oil compositions with dietary fibers to achievethe combined benefits of each. By “dietary fiber” is meant complexcarbohydrates resistant to digestion by mammalian enzymes, such as thecarbohydrates found in plant cell walls and seaweed, and those producedby microbial fermentation. Examples of these complex carbohydrates arebrans, celluloses, hemicelluloses, pectins, gums and mucilages, seaweedextract, and biosynthetic gums. Sources of the cellulosic fiber includevegetables, fruits, seeds, cereals, and manmade fibers (for example, bybacterial synthesis). Commercial fibers such as purified plantcellulose, or cellulose flour, can also be used. Naturally occurringfibers, such as psyllium, and fibers from whole citrus peel, citrusalbedo, sugar beets, citrus, pulp and vesicle solids, apples, apricots,and watermelon rinds.

These dietary fibers may be in a crude or purified form. The dietaryfiber used may be of a single type (e.g., cellulose), a compositedietary fiber (e.g., citrus albedo fiber containing cellulose andpectin), or some combination of fibers (e.g., cellulose and a gum). Thefibers can be processed by methods known to the art.

Of course, judgment must be exercised to make use of the presentcompositions and combinations thereof with other food ingredients. Forexample, a combination of sweetener and present flowable compositionswould not be used where the specific benefits of the two are notdesired. The composition and flowable composition/ingredientcombinations are used where appropriate, and in appropriate amounts.

Many benefits are obtained from the use of the these nondigestible oilcomposition in food and beverage compositions, either when used alone orin combination with edible oils and/or other ingredients discussedabove. A primary benefit is the calorie reduction achieved whennondigestible oil compositions are used as a total or partial fatreplacement. This calorie reduction can be increased by usingcombinations of the present nondigestible oil compositions with reducedcalorie sweeteners, bulking agents, or other nondigestible fats andoils. Another benefit which follows from this use is a decrease in thetotal amount of digestible fats in the diet. Furthermore, a significantreduction in saturated fat consumption can be achieved by substitutingthe present nondigestible oil compositions for saturated fats in thediet. Foods or beverages made with the nondigestible solid fat materialsinstead of animal-derived triglyceride fats will also contain lesscholesterol, and the ingestion of these foods can lead to reduced serumcholesterol and thus reduced risk of heart disease. Also, compositionsmade with these fat materials have acceptable organoleptic properties,particularly lack of waxiness.

Dietary foods can be made with the nondigestible oil compositions tomeet special dietary needs, for example, of persons who are obese,diabetic, or hypercholesterolemic. The present compositions can be amajor part of a low-fat, low-calorie, low-cholesterol diet, and they canbe used alone or in combination with drug therapy or other therapy.Combinations of food or beverage products made with the presentnondigestible oil compositions can be used as part of a total dietarymanagement regimen, based on one or more of these products, containingthe fat materials alone or in combination with one or more of theabove-mentioned ingredients, to provide one or more of theabove-mentioned benefits.

This discussion of the present nondigestible oil composition uses,combinations, and benefits is not intended to be limiting orall-inclusive. It is contemplated that other similar uses and benefitscan be found that will fall within the spirit and scope of thisinvention.

In addition to food compositions, the flowable or non-flowablenondigestible oil compositions of the present invention can be used informulating lubricants, skin creams, pharmaceuticals, cosmetics, and thelike.

The invention will be illustrated by the examples which follow theanalytical methods.

E. Processing of Flowable Nondigestible Oil into Food and BeverageProducts

The present flowable compositions are useful in the preparation of awide variety of food and beverage products. Because of the processingsteps in the present invention, the resulting flowable nondigestible oilcomposition, if consumed in its form directly or in foods containing theflowable nondigestible oil, may have relatively poor passive oil losscontrol. Consequently, it is important first to completely melt theflowable nondigestible oil to a completely molten nondigestible oil,such that the crystallized solid polyol fatty acid polyester issubstantially completely melted. Preferably, the flowable nondigestibleoil is melted up to a temperature of about 10° C. or more above thecomplete melt point of the solid polyol fatty acid polyester. The moltennondigestible oil can then be processed into food and beveragecompositions in a manner that provides sufficiently rapid cooling of thenondigestible oil in a substantially quiescent state (that is, withoutapplying shear during the crystallization) to yield a solid polyolpolyester crystalline structure that provides good passive oil losscontrol.

Alternatively, the flowable nondigestible oil can be applied into thefood-making process directly, so long as the processing results in asubstantially complete melting of the solid polyol fatty acid polyester,and subsequent rapid cooling of the molten nondigestible oil to providethe good passive oil loss control. An example of such a process isspraying of the flowable nondigestible oil onto the surface of a snackfood just after frying or baking. Because the snack food is still hot,the flowable nondigestible oil will be substantially completely melted,including the solid polyol fatty acid polyester thereof, and willsubsequently crystallize into a form displaying passive oil loss controlas the snack food cools rapidly.

When the flowable nondigestible oil composition comprises a temperaturesensitive food additive, such as a vitamin, then it is important thatthe time during which the nondigestible oil composition is in itsre-melted state should be kept to a minimum to avoid loss of efficacy ofthe vitamin.

F. Analytical Methods

(a). Solid Fat Content

Before determining Solid Fat Content (SFC) values, a sample of theflowable composition or mixture of nondigestible liquid/solid is heatedto a temperature of 140° F. (60° C. ) or higher for at least 30 minutesor until the sample is completely melted. The melted sample is thentempered as follows: at 80° F. (26.7° C. ) for 15 minutes; at 32° F. (0°C.) for 15 minutes; at 80° F. (26.7° C.) for 30 minutes; and at 32° F.(0° C. ) for 15 minutes. After tempering, the SFC values of the sampleat temperatures of 50° F. (10° C.), 70° F. (21.1° C.), 80° F. (26.7°C.), 92° F. (33.3° C.) and 98.6° F. (37° C. ), can be determined bypulsed nuclear magnetic resonance (PNMR) after equilibration for 30minutes at each temperature. The method for determining SFC values byPNMR is described in Madison and Hill, J. Amer. Oil Chem. Soc., Vol. 55(1978), pp. 328-31 (herein incorporated by reference). Measurement ofSFC by PNMR is also described in A.O.C.S. Official Method Cd. 16-81,Official Methods and Recommended Practices of The American Oil ChemistsSociety, 3rd. Ed., 1987 (herein incorporated by reference).

The slope of the SFC profile is calculated by subtracting the percentsolids at 70° F. from the percent solids at 98.6° F. and dividing thatvalue by 28.6.

(b). Consistency

The Consistency (K) of the nondigestible oil is measured at atemperature between 20 and 40° C. using a Rheometrics controlled stressrheometer equipped with a cone and plate measuring system. The conediameter is 4 cm and the cone angle is 2 degrees. A sample of thenondigestible oil is carefully applied to the plate and the cone is thenslowly lowered onto the sample (gap=0.048 mm). A flow measurement isperformed via the programmed application of a shear stress over time.The shear stress is increased from zero to 5,000 dynes/cm² over a 2minutes time span. The applied stress results in deformation of thesample (i.e., strain) and the rate of strain is reported as a shearrate. These data are used to create a flow curve of log [apparentviscosity] versus log [shear rate] for the nondigestible oil sample. Theflow curve is then modeled according to the following power law model:

Apparent Viscosity=K (Shear Rate)^(n−1)

where the apparent viscosity is expressed in units of poise (P), shearrate is in units of 1/sec, K is the Consistency in units ofP.sec^((n−1)), and n is the shear index (dimensionless). The power lawmodel/ms widely used to describe the flow behavior of non-newtonianmaterials. On the log-log plot of apparent viscosity versus shear rate,the power law model is a straight line with slope of (n−1). The shearindex (n) varies from 0 to 1. The closer n is to 1, the closer thematerial's flow behavior is to newtonian behavior. The Consistency (K)is numerically equal to the apparent viscosity at a shear rate of 1sec⁻¹. The values of K and n describe the flow behavior of thenondigestible oil within specific limits of shear.

(c). Crystallization Onset Temperature

The crystallization onset temperature is that temperature at which,under the conditions of this test, turbidity is induced in the samplewithin 90 minutes after reaching and maintaining the crystallizationonset temperature. Turbidity is caused by the first stage ofcrystallization. Apparatus:

1. Jacketed, agitated, cylindrical glass flask, 4 inches in diameter, atleast 250 ml volume. Heating and cooling are accomplished by circulationof a clear, uncolored fluid through the jacket. Acceptable jacket fluidsare, but are not limited to, water, ethylene glycol, or silicone fluids.

2. Thermometer, calibrated in the range 25° C. to 100° C.

Procedure:

1. In the flask, heat at least 250 ml of sample (but not more than 700ml) to 85° C. and hold until all solids have dissolved. Beforeproceeding, the solution must be clear, without any turbidity.

2. Agitate to maintain uniform temperature throughout the flask.

3. Cool at no more than 2.5° C./min to a temperature in the vicinity ofthe crystallization onset temperature. Note: To prevent crystallizationon the vessel walls during cooling, the jacket temperature should neverbe any colder than 5° C. below the sample temperature.

4. Hold at this temperature for 90 minutes or until the clear solutionshows (by viewing horizontally through the vessel wall) the first hintof turbidity.

5. If the solution becomes turbid within 90 minutes, repeat by heatingand redissolving the sample as in step 1. Repeat steps 2, 3, and 4,except cool to a temperature 2° C. above the previous measurement.

6. Repeat until the solution does not become turbid within 90 minutes ofreaching the test temperature. The crystallization onset temperature isthe highest temperature at which the solution becomes turbid within 90minutes.

7. If, on the first measurement, after 90 minutes the solution remainsclear, repeat by heating and re-dissolving the sample as in step 1.Repeat steps 2, 3, and 4, except cool to a temperature 2° C. below theprevious measurement. The crystallization onset temperature is thehighest temperature at which the solution becomes turbid within 90minutes.

(d). Fatty Acid Composition of Polyol Polyesters

The fatty acid composition (FAC) of the polyol polyesters is determinedby gas chromatography, using a Hewlett-Packard Model S712A gaschromatograph equipped with a flame ionization detector and aHewlett-Packard Model 17671A automatic sampler. The chromatographicmethod used is described in Official Methods and Recommended Practicesof the American Oil Chemists Society, 3rd Ed., 1984, Procedure 1-Ce62(incorporated herein by reference).

(e). Ester Distribution of Sucrose Polyesters

The relative distribution of the individual octa-, hepta-, hexa- andpenta- esters, as well as collectively the tetra- through mono-esters,of the sucrose polyesters can be determined using normal-phase highperformance liquid chromatography (HPLC). A silica gel-packed column isused in this method to separate the polyester sample into the respectiveester groupings noted above. Hexane and methyl-t-butyl ether are used asthe mobile phase solvents. The ester groupings are quantitated using amass detector (i.e. an evaporative light-scattering detector). Thedetector response is measured and then normalized to 100%. Theindividual ester groups are expressed as a relative percentage.

(f). Complete Melt Point

Equipment:

Perkin-Elmer 7 Series Thermal Analysis System, Model DSC7, manufacturedby Perkin-Elmer, Norwalk, Conn.

Procedure:

1) Sample of polyol polyester is heated to at least 10° C. above thetemperature at which all visible solids are melted, and mixedthoroughly.

2) 10±2 mg. of sample is weighed into sample pan.

3) A scan is performed from about 10° C. above the temperature at whichall visible solids are melted, to −60° C. at 5° C. per minute.

4) The temperature of the sample is maintained at −60° C. for 3 minutesand scanned from −60° C. to the original starting temperature at 5° C.per minute (i.e. about 10° C. above the temperature at which all visiblesolids are melted).

5) The complete melting point is the temperature at the intersection ofthe baseline (i.e., specific heat line) with the line tangent to thetrailing edge of the last (highest temperature) endothermic peak.

(g). Thickness of Solid Polyol Fatty Acid Polyester Particles (LightMicroscopy)

The thickness of the solid polyol polyester particles formed in theflowable nondigestible oil compositions herein may estimated at roomtemperature with a Nikon Microphot video-enhanced light microscope(VELM) using Hoffman Modulation Contrast (HMC) optics according to thefollowing method:

1. A small portion (i.e., 1-10 mg) of the nondigestible oil sample withthe solid polyol fatty acid polyester particles dispersed therein isplaced on a microscope slide and covered. The slide is placed under themicroscope.

2. The sample is examined using a HMC 100× oil objective as the standardlens in conjunction with a 10× eyepiece lens.

3. A microscope-mounted video camera and associated controller are usedfor video enhancement to facilitate differentiation between the sampleand the background.

4. The thickness of the solid polyol fatty acid polyester particles ismeasured in um (microns).

This method permits differentiation of particles having thicknesses justwithin the resolution of the VELM (approximately 0.2-0.5 um). Particlethickness of particles having smaller dimensions can be determined bythe Freeze Fracture Method described hereinafter.

(Note: No special sample preparation is required, other than obtaining arepresentative sample. The samples should be melted and cooledambiently.) Reference: Robert Hoffman, “The Modulation ContrastMicroscope: Principles and Performances”, Journal of Microscopy, Vol.110, Pt 3, August 1977, pp. 205-222.

(h). Thickness of Solid Polyol Fatty Acid Polyester Particles (FreezeFracture Transmission Electron Microscopy)

The three-dimensional topography of particles of polyol fatty acidpolyesters and their size can be determined by a freeze-fracturetransmission electron microscopy (ff-tem) method.

This freeze-fracture method is carried out as follows:

1. The outside cavity of a freezing container is filled with liquid N₂and the inner dewar of the freezing container is filled with liquidethane (normal melting temperature of −172° C. ). The ethane is allowedto freeze.

2. A small amount (1-2 ul) of the nondigestible fat sample with thesolid polyol fatty acid polyester particles dispersed therein is placedin the well of a gold-plated Balzers specimen holder. (Note: for veryfluid samples, 1-2 ul of sample is placed on a gold planchet (Balzers)and another planchet is placed on top of the first to form a sandwich.)

3. Most of the frozen ethane in the dewar is melted by inserting a metalheat sink into the dewar.

4. Immediately after melting the ethane, the specimen holder containingthe nondigestible fat sample is picked up using a pair of tweezers andrapidly plunged into the liquid ethane.

5. After a few seconds, the specimen holder is removed from the ethane,quickly touched to the tip of a camel's hair brush to remove excessethane, and immediately immersed in the liquid N₂ to keep the samplecold.

6. The sample is transferred under liquid N² to a JEOL JFD-9000C sampleholder and then transferred into the chamber of a JEOL JFD-9000Cfreeze-fracture unit. The temperature of the unit should be about −175°C. Vacuum should be at least 8×10⁻⁷ torr.

7. A knife is cooled to a temperature of about −165° C.

8. The sample is fractured in the JEOL chamber using the pre-cooledknife.

9. Platinum-carbon is deposited onto the fractured sample at a 45° anglefor 4.5 seconds, followed by carbon deposition at a 90° angle for 25seconds to form a replica of the fractured sample. The high voltage is2500V and the current is 70 mA.

10. The samples are removed from the freeze fracture unit and cleanedusing 3 washes of chloroform.

11. The replica is picked up on a 300 mesh copper EM grid and examinedin a transmission electron microscope.

12. Images are recorded on negative film and positive prints are madefrom the negatives.

13. The thickness of the polyol fatty acid polyester particles ismeasured in nm.

References:

Rash, J. E. and Hudson, C. S., Freeze Fracture: Methods. Artifacts, andInterpretations, New Haven Press, New York, 1979.

Stolinski and Breathnach, Freeze Fracture Replication of BiologicalTissues, Academic Press, London, 1975.

Steinbrecht and Zierold, Cryotechniques in Biological ElectronMicroscopy, Springer-Verlag, Berlin, 1987.

Specific Examples

Preparation of flowable nondigestible fat compositions of the presentinvention is illustrated by the following examples.

Example 1

A solid sucrose polyester and a liquid sucrose polyester, having fattyacid compositions and ester distributions typical of those shown inTable C for the product Olean® manufactured by The Procter & GambleCompany, Cincinnati, Ohio, are mixed at a proportion of 6 weight partsof the solid sucrose polyester to 94 weight parts of the liquid sucrosepolyester, and agitated to a molten liquid state at a temperature of 68°C. in a temperature controlled agitated vessel. This molten mixture isthen pumped at a flow rate of 280 pounds per hour (127.3 kg/hr) throughtwo serially-arranged brine-jacketed (−1.0° C. brine coolant) CherryBurrell Votator Model 3SSHE scrapped wall heat exchangers, operating at1690 RPM. The temperature of the mixture is lowered from 68° C. to 21°C. within a residence time of 20 seconds. Upon exiting the CherryBurrell heat exchangers, the solid sucrose polyester portion issubstantially crystallized and forms small (<10 micron) discrete andunaggregated crystal particles. The substantially crystallizedcomposition is then passed through a heat exchanger which adjusts thetemperature (as needed) to 21° C., and into a jacketed scraped wall tankwhere it is held under continued shearing for two hour at 21° C. Thebatch tempering tank is 12 inches in diameter and 28 inches deep, holds100 pounds (45.5 kg) of the composition, and is equipped with ananchor-type agitator which turns at 14 rpm; there are no dead spots inthe material in the vessel.

The resulting flowable nondigestible oil product has the followingphysical attributes:

heat exchanger outlet and continued shearing hold temperature: 21° C.

shear index: n=0.6

Consistency (70° F.):60 P.sec^((n−1))

Example 2

The Example #1 is repeated, except for changes in the scraped wall heatexchanger outlet temperature, as shown in Table A.

TABLE A Scraped wall heat exchanger outlet temperature 15.5° C. 21° C.26.7° C. 39.4° C. Consistency (K) 63 60 60 63 shear index (n) 0.6 0.60.7 0.5

Example 3

The Example #1 is repeated, except for changes in the tempering time andthe scraped wall heat exchanger outlet temperature, as shown in Table B.

TABLE B Scraped wall heat exchanger Continued shearing Consistency shearindex outlet temperature time, minutes (K) (n) 21° C. 30 90 0.5 60 800.6 120  62 0.6 15.6° C. 30 75 0.6 60 75 0.6 120  67 0.6

TABLE C Fatty Acid Composition and Ester Distribution of the SolidSucrose Polyester and the Liquid Sucrose Polyester Components of Olean ®Solid Sucrose Liquid Sucrose Fatty Acid Polyester Polyester Component(weight %) (weight %) C8 — — C10 — — C12 0 — C14 0 — C16 1.2 9.7 C17 00.1 C18 4.6 5.9 C18:1 3.7 64.5 C18:2 10.9 18.9 C18:3 0 0.2 C20 4.6 0.3C22 71.7 0.2 C22:1 0.2 — C24 2.8 — Other 0.4 0.2 Ester Distribution. % %Octa 71.6 78.7 Hepta 28.2 21.0 Hexa 0.2 0.2 Penta <0.1 0.2 Lower <0.10.1

What is claimed is:
 1. A process for making a flowable nondigestible oilcomposition comprising a liquid polyol fatty acid polyester having acomplete melt point less than 37° C., and a solid polyol fatty acidpolyester having a complete melt point of at least about 37° C., theprocess comprising the steps of: a) melting the nondigestible oilcomprising the solid polyol fatty acid polyester and the liquid polyolfatty acid polyester, b) crystallizing at least a substantial portion ofthe solid polyol fatty acid polyester, wherein said crystallizingfurther comprises continued holding the crystallized composition at acrystallization temperature whereby the crystallization of the solidpolyol fatty acid polyester is substantially complete, and furtherwherein the crystallization temperature is about 5° C. or more below theonset crystallization temperatures of the solid polyol fatty acidpolyester, and c) shearing the nondigestible oil composition during thestep of crystallizing, thereby forming the solid polyol fatty acidpolyester into crystallized particles, wherein the flowablenondigestible oil has a Consistency in a temperature range of 20° to 40°C. of less than about 600 P.sec^((n−1)).
 2. The process according toclaim 1 wherein the step b) of crystallizing comprises the steps of: i)reducing the temperature of the melted nondigestible oil to acrystallization temperature less than the onset crystallizationtemperature of the solid polyol fatty acid polyester, and ii) holdingthe nondigestible oil at the crystallization temperature for a timesufficient to crystallize at least a substantial portion of the solidpolyol fatty acid polyester.
 3. The process according to claim 1 whereinthe shearing step c) further comprises continued shearing of thecomposition during the continued holding step.
 4. The process accordingto claim 1 wherein the flowable nondigestible oil composition has aConsistency in a temperature range of 20°-40° C. of less than about 400P.sec^((n−1)).
 5. The process according to claim 4 wherein theConsistency in a temperature range of 20°-40° C. is less than about 200P.sec^((n−1)).
 6. The process according to claim 5 wherein theConsistency in a temperature range of 20°-40 C. is less than about 100P.sec^((n−1)).
 7. The process according to claim 1 wherein the solidpolyol fatty acid polyester has a complete melt point of at least 60° C.8. The process according to claim 7 wherein the solid polyol fatty acidpolyester is selected from the group consisting of (i) a solid saturatedpolyol polyester, (ii) a solid diversely esterified polyol polyester,(iii) a polyol polyester polymer, and (iv) combinations thereof.
 9. Theprocess according to claim 8 wherein the solid polyol fatty acidpolyester comprises a solid saturated polyol polyester comprisingocta-behenate sucrose polyester, and a solid diversely esterified polyolpolyester comprising octa-saturated sucrose polyester wherein the estersare selected from behenate and a mixture of C8:1 and C18:2 unsaturate.10. The process according to claim 1 wherein the crystallized particlesof solid polyol fatty acid polyester have a maximum dimension of about 1micron to about 30 microns.
 11. The process according to claim 1 whereinin step b) at least 80% of the solid polyol fatty acid polyester iscrystallized.
 12. The process according to claim 11 wherein in step b)at least 95% of the solid polyol fatty acid polyester is crystallized.13. The process according to claim 11 wherein the step of crystallizingthe solid polyol fatty acid polyester is at a crystallizing temperatureof at least about 10° C. below the onset crystallization temperature ofthe solid polyol fatty acid polyester.
 14. The process according toclaim 13 wherein the step b) of crystallizing comprises cooling thecomposition from the molten temperature to the crystallizationtemperature at a cooling rate of about 100-300° C./min.
 15. The processaccording to claim 14 wherein step b) is completed within about 30seconds.
 16. The process according to claim 15 wherein step c) comprisesshearing the crystallizing composition at a shear rate of about 400sec⁻¹ to about 8000 sec⁻¹.
 17. The process according to claim 6 whereina diluting amount of the liquid polyol polyester is added to thecrystallized composition in a ratio of from about 0.5:1 to about 0.1:1.18. The process according to claim 17 wherein the steps b) ofcrystallizing and step c) of shearing are both conducted in a scrapedwall heat exchanger or equivalent.
 19. The process according to claim 1further comprising the step of tempering the flowable nondigestible oilcomposition by reducing the temperature to the composition to atempering temperature which is below an intended storage temperature,and shearing the tempering composition.
 20. The process according toclaim 1, further comprising the step of adding a stabilizing amount of adiluent liquid after the step b) of crystallizing the solid polyol fattyacid polyester.